Nitramines



United States Patent Milton B. Frankel, Pasadena, and Karl er, Monrovla, CaliL, assignors to Aerojet-General Corporation, Amsa, Califl, a corporation 'of Ohio No Drawing. Filed Mar. 7, 1957, Ser. No. 644,692 Claims. (Cl. 260-583) invention relates to new compositions of matter and a method for their preparation. In particular, this invention relates to nitramines having the general formula:

plosive missile, projectile, rocket, or the like, as the main:

explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives of this invention in a device such as that disclosed in United States Patent No. 2,470,162, is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufiiciently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The compounds of this invention are readily prepared by reacting the corresponding amine with nitric acid, as illustrated by the general reaction scheme set forth below:

wherein R and A are as defined above.

The amines used as starting materials in this invention are readily obtained by the condensation of primary amines with 2,2-dinitro-1,3-propanediol, as disclosed in our copending application Serial No. 419,616, filed March 29, 1954, now abandoned.

To more clearly illustrate this invention, the following examples are presented. It should be understood, however, that these examples are presented merely as a means of illustration and are not intended to limit the scope of the invention in any way.

EXAMPLE I Preparation of I,1,1,4,6,6,8,11,I1,11-decanitr04,8- diaza undecane A solution of 40 ml. of 100% nitric acid and 40 ml. of acetic anhydride was cooled to a temperature of 5' C. and 4.1 gm. of l,l,l,6,6,ll,ll,ll-octanitro-4,8 -diaza undecane was added. 0n warming to room temperature the solid dissolved. The solution was poured onto ice ice causing a cream-colored gummy solid to precipitate. The product was washed with water and dried. Recrystallization from concentrated nitric acid gave white needles, M.P. 135-137 C., exhibiting an impact stability of 10-15 cm./2 kg. The elemental analysis of the product is as follows:

Calculated for C l-1 N 0 Percent C, 17.77; percent H, l.99; percent N, 27.64. Found: Percent C, 18.29; percent H, 2.02; percent N, 27.40.

The product had a calculated heat of combustion of 20.44 caL/gm. and was foundto be 1984 caL/gm. The explosive power of this compound is as follows:

Lead block value, 177; T.N.T.=l00 Ballistic mortar value, 155; T.N.T.=100

EXAMPLE 11 Preparation of 2,2,5,7,7,9,12,I2-octanitra-5,9-aza tridecane 2,2,5,7,7,9,l2,l2-octanitro-5,9-aza tridecane was prepared by treating 2,2,7,7,12,12 hexanitro 5,9-aza-tri:

decane with nitric acid in the manner described in Example I. The product, recrystallized from ethylene dichloside, had a M.P. of 137-139 C. The elemental analysis of the product is as follows:

Calculated for C H N O Percent C, 24.18; percent H, 3.32: percent N, 25.64. Found: Percent C, 24.76; percent H, 3.44; percent N, 25.52.

This compound had a calculated heat of combustion of 2879 cal./gm. and was found to be 2897 caL/grn.

The explosive power of this compound is as follows:

Lead block value, 128; T.N.T.= Ballistic mortar value, T.N.T.= 100 We have also found that amines such as 2,2,83,14,14- hexanitro-6,l0-diaza pentadecane, 4,4,9,9, 14,14-hexanitro- 7,1l-diaza heptadecane, 2,2,6,6,l0,10-hexanitro-4,8-diaza undecane, l,l,1,$,5,9,9,9-octanitro-3,7-diaza nonane and 2,l6-dimethyl-3,3,9,9,1$,l5-hexanitro-7,l l-diaza heptadecane readily undergo nitration with nitric acid to form their corresponding nitramines, namely, 2,2,6,8,8, 10,14,14- octanitro-6,l0-diaza pentadecane, 4,4,7,9,9,11,14,14-octanitro-7,ll-diaza heptadecane, 2,2,4,6,6,8,10,10-octa.nitro- 4,8-diaza undecane, 1,l,l,3,5,5,7,9,9,9-decanitro 3,7 diiaza nonane, and 2,l6-dimethyl-3,3,7,9,9,11,15,15-ootanitro-7,l l'diaza heptadecane.

It is apparent that any nitramine of the disclosed series can be prepared by merely selecting an appropriate amine and reacting it with nitric acid, in accordance with the teachings of this invention.

We claim: 1. As compositions of matter, nitramines having the formula:

N0, Nos NO: If): N01 R+CHIA-N-CHr-(:JCHs-NACBri -11 N0; N0 N0.

nitramines having the formula:

NO: N01 NO: NO| NO: R--OHr-A-bl-Cflr- -cn,- -A-cH,-o-a

0t on t 8.000.051, r v 7 r 3 MinkisnloweraikylredicalandAisalower alkylemradisal.

4. \AS a composition of matter, l,1,l,4,6,6,8,11,11,11- decanitro-4,8diz.za undecane having rhe structural for- 5. As a composition of matter, 2,2,5,7,7,9,12.12-octanflm-SS-diaza u'idecane having the structural formula:

6. The method of preparing min-amines having the formula:

hich corr prises reacting nitric acid with an amine having the tonnul wherein R is a radical selected from a group consisting of lower alkyl and nitro radicals and A is a lower alkylene E. The method of preparing nitramines having the formula:

which comprises reacting nitric acid with an amine having the formula:

N01 N01 N61 NOr---CHr-A-NH-CHr-'-CH:-NHACHrNO1 N01 N 01 N01 wherein A is a. lower alkylene radical.

ammerhedotm nimmiwhwingtbe flea-mm:

which comprises reacting nitric acid with an amine having fhe'fcrmula:

NO} ND: ND; n o-om-i-mfl-oar-kcar-im-n-cm-Ln rlro, N0: N0.

WIBIEI IIRBQWWIMMABIW alkylcneradicel. 

1. AS COMPOSITIONS OF MATTER, NITRAMINES HAVING THE FORMULA: 